PMID- 38040258 OWN - NLM STAT- MEDLINE DCOM- 20240110 LR - 20240110 IS - 1879-1298 (Electronic) IS - 0045-6535 (Linking) VI - 349 DP - 2024 Feb TI - Evolution of chlorinated paraffin and olefin fingerprints in sewage sludge from 1993 to 2020 of a Swiss municipal wastewater treatment plant. PG - 140825 LID - S0045-6535(23)03095-3 [pii] LID - 10.1016/j.chemosphere.2023.140825 [doi] AB - Exposure of humans to chlorinated paraffins (CPs) and chlorinated olefins (COs) can occur via contact with CP-containing plastic materials. Such plastic materials can contain short-chain CPs (SCCPs), which are regulated as persistent organic pollutants (POPs) under the Stockholm Convention since 2017. Municipal wastewater treatment plants (WWTP) collect effluents of thousands of households and their sludge is a marker for CP exposure. We investigated digested sewage sludge collected in the years 1993, 2002, 2007, 2012, and 2020 from a Swiss WWTP serving between 20000 and 23000 inhabitants. A liquid chromatography mass spectrometry (R > 100000) method, in combination with an atmospheric pressure chemical ionization source (LC-APCI-MS), was used to detect mass spectra of CPs and olefinic side products. A R-based automated spectra evaluation routine (RASER) was applied to search for approximately 23000 ions whereof approximately 6000 ions could be assigned to CPs, chlorinated mono- (COs), di- (CdiOs) and tri-olefins (CtriOs). Up to 230 CP-, 120 CO-, 50 CdiO- and 20 CtriO-homologues could be identified in sludge. Characteristic fingerprints were deduced describing C- and Cl-homologue distributions, chlorine- (n(Cl)) and carbon- (n(C)) numbers of CPs and COs. In addition, proportions of saturated and unsaturated material were determined together with proportions of different chain length classes including short- (SC), medium- (MC), long- (LC) and very long-chain (vLC) material. A substantial reduction of SCCPs of 84% was observed from 1993 to 2020. Respective levels of MCCPs, LCCPs and vLCCPs decreased by 61, 69 and 58%. These trends confirm that banned SCCPs and non-regulated CPs are present in WWTP sludge and higher-chlorinated SCCPs were replaced by lower chlorinated MCCPs. Combining high-resolution mass spectrometry with a selective and fast data evaluation method can produce characteristic fingerprints of sewage sludge describing the long-term trends in a WWTP catchment area. CI - Copyright (c) 2023 The Authors. Published by Elsevier Ltd.. All rights reserved. FAU - Knobloch, Marco C AU - Knobloch MC AD - Swiss Federal Institute for Materials Science and Technology Empa, Laboratory for Advanced Analytical Technologies, Uberlandstrasse 129, 8600, Dubendorf, Switzerland; University of Zurich, Department of Chemistry, Winterthurerstrasse 190, 8057, Zurich, Switzerland. FAU - Hutter, Jules AU - Hutter J AD - Swiss Federal Institute for Materials Science and Technology Empa, Laboratory for Advanced Analytical Technologies, Uberlandstrasse 129, 8600, Dubendorf, Switzerland; Zurich University of Applied Sciences ZHAW, Einsiedlerstrasse 31, 8820, Wadenswil, Switzerland. Electronic address: jules.hutter@empa.ch. FAU - Diaz, Oscar Mendo AU - Diaz OM AD - Swiss Federal Institute for Materials Science and Technology Empa, Laboratory for Advanced Analytical Technologies, Uberlandstrasse 129, 8600, Dubendorf, Switzerland; University of Zurich, Department of Chemistry, Winterthurerstrasse 190, 8057, Zurich, Switzerland. FAU - Zennegg, Markus AU - Zennegg M AD - Swiss Federal Institute for Materials Science and Technology Empa, Laboratory for Advanced Analytical Technologies, Uberlandstrasse 129, 8600, Dubendorf, Switzerland. FAU - Vogel, Jean Claude AU - Vogel JC AD - Office for Waste, Water, Energy and Air of the Canton of Zurich AWEL, Water Protection Department, Hardturmstrasse 105, 8090, Zurich, Switzerland. FAU - Durisch, Edith AU - Durisch E AD - Office for Waste, Water, Energy and Air of the Canton of Zurich AWEL, Water Protection Department, Hardturmstrasse 105, 8090, Zurich, Switzerland. FAU - Stalder, Urs AU - Stalder U AD - University of Zurich, Department of Chemistry, Winterthurerstrasse 190, 8057, Zurich, Switzerland. FAU - Bigler, Laurent AU - Bigler L AD - University of Zurich, Department of Chemistry, Winterthurerstrasse 190, 8057, Zurich, Switzerland. FAU - Kern, Susanne AU - Kern S AD - Zurich University of Applied Sciences ZHAW, Einsiedlerstrasse 31, 8820, Wadenswil, Switzerland. FAU - Bleiner, Davide AU - Bleiner D AD - Swiss Federal Institute for Materials Science and Technology Empa, Laboratory for Advanced Analytical Technologies, Uberlandstrasse 129, 8600, Dubendorf, Switzerland; University of Zurich, Department of Chemistry, Winterthurerstrasse 190, 8057, Zurich, Switzerland. FAU - Heeb, Norbert V AU - Heeb NV AD - Swiss Federal Institute for Materials Science and Technology Empa, Laboratory for Advanced Analytical Technologies, Uberlandstrasse 129, 8600, Dubendorf, Switzerland. LA - eng PT - Journal Article DEP - 20231129 PL - England TA - Chemosphere JT - Chemosphere JID - 0320657 RN - 0 (Hydrocarbons, Chlorinated) RN - 0 (Sewage) RN - 8002-74-2 (Paraffin) RN - 0 (Halogens) RN - 0 (Ions) SB - IM MH - Humans MH - *Hydrocarbons, Chlorinated/analysis MH - Sewage/analysis MH - Paraffin/analysis MH - Switzerland MH - Environmental Monitoring/methods MH - Halogens/analysis MH - *Water Purification MH - Ions/analysis MH - China OTO - NOTNLM OT - Chlorinated olefins (COs) OT - Chlorinated paraffins (CPs) OT - Fingerprinting OT - Orbitrap mass spectrometry OT - Persistent organic pollutants (POPs) OT - RASER (R-based automated spectra evaluation routine) COIS- Declaration of competing interest All authors declare that there are no conflicts of interest. EDAT- 2023/12/02 00:42 MHDA- 2024/01/10 06:42 CRDT- 2023/12/01 19:29 PHST- 2023/10/05 00:00 [received] PHST- 2023/11/23 00:00 [revised] PHST- 2023/11/26 00:00 [accepted] PHST- 2024/01/10 06:42 [medline] PHST- 2023/12/02 00:42 [pubmed] PHST- 2023/12/01 19:29 [entrez] AID - S0045-6535(23)03095-3 [pii] AID - 10.1016/j.chemosphere.2023.140825 [doi] PST - ppublish SO - Chemosphere. 2024 Feb;349:140825. doi: 10.1016/j.chemosphere.2023.140825. Epub 2023 Nov 29.